JPS61155272A - Manufacture of ceramic structure - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application of Industry-1 The present invention relates to a method for producing a ceramic 4'+'J structure. More specifically, the present invention relates to a method for producing a porous ceramic structure useful for collecting carbon fine particles contained in the exhaust gas of a tea cell internal combustion engine or as a catalyst carrier.

[Prior Art 7] Conventionally, as a method for manufacturing porous ceramics, a method is known in which a ceramic slurry is attached to an organic polymer foam, such as a polyurethane foam from which the cell membrane has been completely removed, followed by drying and firing. No. 55-111817, same 2
4585) j In addition, as a method for producing a porous ceramic having a plurality of columnar hollow holes parallel to each other (adjacent hollow holes open in opposite directions), JII7 produces the same shape as the ceramics described in -1. The organic compound foam obtained by foaming an organic compound with a three-dimensional network skeleton in the mold cavity is subjected to film removal treatment to form a ceramic slurry.
A method of impregnating, drying, and firing is also known (Japanese Unexamined Patent Publication No. 5
8-161962).

"Problem to be Solved by the Invention 2] The organic polymer foam used to produce such porous ceramics is required to have no cell membrane, and in the case of polyurethane mold foam, chemical (alkali) or heat ( It is necessary to completely remove the cell membrane through a combustion process, and with conventional polyurethane mold foams, this membrane removal process takes a long time, and the process is too long. There are problems such as breakage, and there is a demand for a method that does not require such membrane removal treatment or can produce a porous ceramic that can provide a sufficient membrane removal effect with a short membrane removal treatment.

Means for Solving Problem C] According to the present invention, by using a specific silicone foam stabilizer and a tertiary amine catalyst, a skinless polyurethane foam with less cell membranes can be obtained, and the above-mentioned porous polyurethane foam can be obtained. Manufacturing of ceramics, especially JP-A-58-161962
It was found to be useful with bows.

That is, the present invention involves applying a ceramic slurry to an organic polymer foam, drying it, and firing it to produce a porous ceramic structure. 1 formula chunin represents a polyoxyethylene chain with an average molecular weight of 1100 to 700, 1: and/or oxypropylene chain, X represents 3 to 20, y represents 3 to 30, and ■ < is H
O, L, and/or an alkyl group having 1 to 5 carbon atoms and/'
Or represents an acyl group. (However, dimethylsiloxane) and polyoxyalkylene siloxane units may be randomly arranged. )] A method for producing a ceramic structure (first invention), characterized by using a polyurethane foam formed by mold foaming in the presence of a silicone 4-foaming agent, a tertiary amine catalyst, and a blowing agent (σ); A plurality of columnar hollow holes parallel to each other are provided inside the ceramic so as to form a lattice-like arrangement in a cross section perpendicular to the axis of the hollow holes, and one end of the columnar hollow holes is opened to one end surface of the ceramic. , the other end is sealed at the other end face of the ceramic, and adjacent columnar hollow holes are opened in opposite directions across the hollow hole walls arranged in a lattice pattern. , the mold container part is formed of an end face and a side wall to which a columnar member is fixed for forming a group of columnar hollow holes opening in the same direction, and the other end face is opened in the same direction; The cavity of the mold formed by engaging the mold lid to which the columnar member for forming the columnar hollow hole group is fixed has the same shape as the ceramic described in 1. In the cavity, an organic polyisocyanate and a polyol are foamed in the presence of a silicone foam stabilizer represented by the general formula (11), a tertiary amine catalyst, and a blowing agent to obtain a foam having the same shape as the -C ceramics.
Then, a ceramic slurry is added to the foam obtained in the above step.
This is a method for producing a porous ceramic structure (second invention) characterized by comprising two steps of impregnating the porous ceramic structure, drying it, and firing it.

In the general formula (1) of the foam stabilizer used in the present invention, one alkyl group includes methyl, ethyl, I]- and one alkyl group.
Acyl groups such as -propyl and butyl include acetyl, propionyl, butyryl, and valeryl.

In general formula (1), A includes a polyoxyethylene chain, a polyoxypropylene chain, and a polyoxyethylene oxypropylene chain.

Among these, polyoxyethylene oxypropylene chains, especially those mainly composed of oxypropylene groups (oxybu "1 pyrene/oxyethylene weight ratio 50:50~
99:1, more preferably 80:20-99:'1)
is preferred.

As the silicone foam stabilizer represented by the general formula (), a polyoxyalkylene siloxane copolymer soluble in the above polyol is suitable. L-5809 (IE Book 5: Car (product name of Kawa), product name of B-5246 (Goldschmidt)) SI-1-193, SRX-27
4C (trade name of Toray Silicone) can be mentioned. The silicone foam stabilizer is Polyol 100
It is generally used in an amount of 0.5 to 1.5 parts, preferably 0.6 to 10 parts. If the amount is less than 0.5 parts, the resulting mold foam will have roughened cells, and if it is more than 15 parts, the mold foam will have an extremely large amount of surface skin.

The tertiary amine used as a catalyst in the present invention includes a tertiary amine that promotes a resin formation reaction, a tertiary amine that promotes a foaming reaction, and especially a combination system of both.

Tertiary amines that promote the resin formation reaction include those effective as catalysts for the reaction between alcohol and isocyanate, such as triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, 1,8-diaza-bicyclo ``5゜4 , OJ Lousensen-7, dimethylaminopropylamine, and organic acid salts thereof.

Preferred is] lyethylenediamine.

Tertiary amines that promote the foaming reaction include those that are effective as catalysts for the reaction between water and monoisocyanate, such as N.
-Methylmorpholine, N-ethylmorpholine, triethylamine, chetylethanolamine, siezylethanolamine, and the like. Preferred is N-ethylmorpholine.

The amount of the resinization catalyst used is usually 0.02 to 0.02 parts, preferably 0.02 to 0.02 parts, per 100 parts (by weight, same hereinafter) of the polyol.
05 to 01 parts. If the amount is less than 10.02 parts, the resin formation reaction will be slow and curing will take a long time. Moreover, if it exceeds 0.2 parts, a skin will easily form on the surface of the mold form, resulting in poor air permeability. The amount of blowing catalyst is usually 02 to 09 parts, preferably 04 to 06 parts, per 100 parts of polyol. 02
If the temperature is less than
More skins.

If the amount is more than 0.9 parts, the foaming will be too fast, the foam cells will become fine, and the air permeability will deteriorate. The ratio of the resin forming catalyst to the foaming catalyst is usually 8:97:50:50, preferably 10:90 to 20:80. The total amount of both is usually 0.3 to 1.0 per 100 parts of polyol.
Department.

The amount of catalyst used is the same as that of normal urethane foam.
It is preferable to set it to L.

As the polyol used in the present invention (J, as at least a part of the 11f h in ethylenically unsaturated
L-polyether polyol O3-sterol polyol is a polymer polyol made from small-polyether polyol.
Preference is given to using (A), also i, 1(A), 1, and polyether polyols (B).

The raw materials for polymer polyol (A) are polyether polyol and polyester polyol, both of which are commonly used as polyurethane polymers.
1: The following polyester polyols:
(B) and (C) J can be made in 1 history. These can be conveniently used alone or as a mixture, or they can be mixed with a small amount (polyol composition: usually 20% or less in IN) of low-molecular-weight polyols (described later) to produce polymer polyols. Even”: Yes.

The ethylenically unsaturated monomer (1) used in the production of the polymer polyol (A) used in the present invention includes:
The following may be mentioned: (1) Acrylic acid, methacrylic acid and derivatives thereof: acrylonitrile, methacrylonitrile.

Acrylic acid, methacrylic acid and their salts.

Methyl acrylate, methyl methacrylate, dimethylaminoethyl methacrylate I/-1-, acrylamide, methacrylic acid amide, etc.

('')%' Fj group vinyl Llii styrene,
a-methylstyrene, etc.

(tri) Olefinic hydrocarbon monomer: ethylene,
Propylene, butadiene, inbutylene, isof)non, 1,4-pentadiene, etc.

(1v) Vinyl left stell monomer: vinyl acetate, etc.

(V) Vinyl halide monomer: hinyl chloride, hinyritene chloride, etc.

(vi) Vinyl ether 14Ha form: vinyl methyl ether, etc.

Among these, preferred is acrylonitrile.

These are methyl methacrylate, styrene, and butadiene. Particularly preferred is acrylonitrile, or a combination of acrylonitrile and styrene (styrene:acrylonitrile weight ratio of 10:90 to 60:40).

Polyol in polymer polyol (A), polyether polyol, I: and/or polyester polyol and, if necessary, low-molecular polyol (741m)
The proportion of the ethylenically unsaturated monomer (or polymer) to be used can be varied over a wide range, but usually 2 to 70 parts by weight of the ethylenically unsaturated monomer (or polymer) per 100 parts of the polyol, preferably 17<5.
~40 Jusatobe.

The production of polymer polyols from polyols and ethylenically unsaturated monomers can be carried out by conventional methods. For example, in a polyol, an ethylenically unsaturated monomer is polymerized with a catalyst (
A method of polymerization in the presence of a radical generator, etc.) (U.S. Patent No. 8888351, Japanese Patent Publication No. 89-24787, Japanese Patent Publication No. 47-47999, Japanese Patent Publication No. 15894-1988)
Alternatively, there is a method (Japanese Patent Publication No. 47-47597) in which a polymer obtained by pre-polymerizing the above monomers and a polyol are graft-polymerized in the presence of a radical generator. The former method is preferred. As the polymerization catalyst (radical generator) used in the polymerization reaction, azo compounds, peroxides, persulfates, perborates, etc. can be used, but Practical-1 aso compounds are preferred. Its use is not particularly limited, for example, ethylenically unsaturated monomer (or polymer)
The amount is 01 to 20 parts by weight [1'L parts, preferably 01 to 15 parts by weight, per 100 parts by weight. The polymerization described in -1- can also be carried out using solvents such as toluene, xyene, etc.
You can also f. The reaction temperature is usually 50-17 (+'
1, preferably 90 to 150°' ().

In the present invention, at 45, the combination C with polymer polyol (A)
The polyether polyol (13) used,
Examples include compounds having a structure in which an alkylene oxide is added to a polyfunctional compound containing an active hydrogen atom, such as tl, monohydric alcohol, polyhydric phenol, polycarphonic acid, and an amine compound. The above polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol,
■ Dihydric alcohols such as 6-hexanediol, diethylene glycol, and neopentyl glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol, sorbitol, and sucrose. Examples of polyhydric phenols include polyhydric phenols such as pyrocalol and hydroquinone, bisphenols such as hisphenol A, novolac resins having two or more phenolic hydroxyl groups, and intermediates of resol resins; and polycarphonic acids. As succinic acid,
Examples include aliphatic polycarboxylic acids such as adipic acid, phthalic acid, terefucolic acid, and aromatic polycarboxylic acids such as 1-limellitic acid. Also, as an amine compound, 4f
r-'' For example, monoamines such as ammonia and phthylamine; aliphatic polyamines such as ethylenecyamine, hexamethylenediamine, and diethylene 1-liamine; alicyclic polyamines such as cyclohexylenediamine and inphorondiamine, and phenylenediamine. , l.

Aromatic polyamines such as lylene diamine, xylene amine, diphenyl, methanediamine, polyphenylmethane polyamine, diethyl 1-lylene cyamine; heterocyclic polyamines such as piperazine, N-aminoethylpiperazine; and monoethanolamine, jetanolamine and alkanolamines such as triethanolamine. -1 series of active hydrogen atom-containing compounds are 2
More than one species can also be used. Examples of the alkylene oxide to which f=J is added to the active hydrogen atom-containing compound include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, and epichlorohydrin. The alkylene oxides may be used alone or in combination of two or more, and in the latter case, block addition, random addition, or a mixture of both may be used. More preferred among these alkylene oxides are propylene oxide and/or ethylene oxide, but depending on the required performance, small amounts of other alkylene oxides (butylene oxide, tetrahydrofuran, styrene oxide, etc.) may be used in combination with these. good. From the viewpoint of reactivity, a combination system of propylene oxide and ethylene oxide (usually 7 by weight) is preferable.
0:80-95:5, especially 80:20-90:
10). The addition of alkylene oxides can be carried out in the usual manner, either without catalyst or in the presence of a catalyst (alkali, amine, acid) (particularly in the latter stages of the alkylene oxide addition) at normal pressure. or carried out under pressure.

The OH value of polyether polyol (n) is usually 10 to 7.
01 is preferably 20-50. If the OH number is less than 10, the foam becomes too soft and the shape retention of the molded product becomes poor. If the OH number is 70 or more, there are many skins and cell membranes on the mold surface, resulting in a foam with poor air permeability. The (average) number of functional groups in (B) is usually 2 to 8, preferably 2 to 4.

Among (B), preferred are those having an oxyethylene chain at the end [chip type, balanced type, and random chip type (having a random polyoxyethylene/oxypropylene chain inside)-1.

The content of terminal oxyethyl non-groups is usually 5% (by weight, the same applies hereinafter) or less, preferably 5 to 30%, and more preferably 10 to 20%. Oxyethylene chain content is 5%
If it is less than that, curing immediately before the end of foaming will be insufficient and the foam will collapse. The total oxyethylene group content is usually 5~
50% preferably io to 30%.

In the present invention, it is preferable to use polymer polyol (A) or (A) and polyether (I3) as at least a part of the polyol, but when used in combination (A) and (B ) is preferably 7.
0.30~2080, more preferably 60,40~
30 Near 0. Particularly preferred Ha' 50: 50
, z40.60.

In the present invention, in place of these polyols [(A), (A, ), (B)), other polyols such as polyester polyols ( C), low molecular polyol (1)),
Low molecular weight polyamines (E) can be used.

Examples of polyester polyols (C) include low molecular polyols (or polyether polyols), dicarboxylic acids (or dicarboxylic acid anhydrides,
Examples include condensed polyester polyols obtained by reacting with non-oxide) and polyester polyols obtained by Ichikawara Mi reaction of lactones. Note: Low-molecular polyols include diols such as ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, his(hydroxyethyl)benzene, trimethylolpropane,
Examples include glycerin and mixtures thereof. Dicarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid,
Mention may be made of terephthalic acid, dimer acid and mixtures thereof. Examples of lactones include ε-caprolactone. Among (C), the preferable terminal is grade 0
11 and is liquid at room temperature. From the viewpoint of workability, polyether polyol is preferred.

As the low molecular polyol (B)), the above [, (B)'
+ Dihydric alcohol listed as a raw material for (C), 31
Polyhydric alcohols (glycerin, etc.) with 1ITi or more, alkanolamines (+-liethanolamine, jetanolamine, etc.), and low-molecular polyether polyols with molecular M600 or less are generally used as chain extenders and crosslinking agents (for cars). There are many things that can be mentioned.

The low-molecular polyamine (E) -○ includes the above-mentioned aliphatic, alicyclic, aromatic and heterocyclic polyamines (listed as raw materials for rg).

The proportion of (A) in the total amount of polyol is usually 20% or more, preferably 30-70%, more preferably 40-50%.
%. If (A) is less than 20%, the cell membrane and surface skin of the foam will increase. Moreover, if it exceeds 70%, the cells of the foam partially collapse, which is not preferable. The proportion of (I3) in the total amount of polywords is good l′, and shi< is 3()~
It is preferably 80%, more preferably 40 to 70%, particularly preferably 50 to 60%. The proportion of (C) is usually 50% or less, preferably 30% or less, the proportion of (D) (including the amount if a low molecular polyol is used in conjunction with the production of the polymer polyol) is usually 20% or less, Preferably it is 10% or less. The amount of (E) is usually 5% or less, preferably 3% or less.

The proportion of the polymer portion in (A) contained in the total amount of polyol is usually 5 to 40%, preferably 10 to 20%.

Entire polyol 1.1 (A) polyol portion and (
The terminal oxyethylene group content (average) of 13)) is preferably 5% or more (5 to 30%), particularly 10 to 20%.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. For example, aliphatic polyisocyanates (hexamethylene diisocyanate, lysine diisocyanate, etc.), alicyclic polyisocyanes 1-, cyclohexylmethane diisocyanates 1-, isophorone diisocyanates 1-, aromatic polyinsocyanates [tolylene diisocyanates] TDI), diphenylmethane diisocyanate (MI)), naphthylene diisocyanate, xylylene diisocyanate (1), etc.] and mixtures thereof. Among these, aromatic diisocyanes are preferable, and TDI is preferable for running.
It is MDI. These polyisocyanates are crude polyisocyanates such as crude TDLifl MDI (
Diadiaminodiphenylmethane manufactured by lfi 1 Formaldehyde Coupling product with aromatic amine or mixture thereof: Poskene compound of diaminodiphenylmethane and a mixture of trifunctional or higher-1 polyamine with a small amount of 1IV (e.g. 5 to 20% by volume) Polyaryl Boriison Ane-1- (PAp
l) J-((4th use can also be used. Or modified polyisocyanate-1, for example, liquefied A1
1H (carbozyimito-modified, i.lihytrope-1-modified, etc.) and excess polyison blue, -
1-(i″I'l I, hl 1') Imatoko(
. For example, it is also possible to combine the prepolymer with modified polyisocyanate-1. The polyol used in the above prepolymer production is a polyol having an equivalent weight, usually +30 to +200°, such as glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol, and triols such as trimethylolpropane and chrycerin.

Highly functional polyols such as pentaerythritol, sorbitol, and sodium; and alkylene oxide (ethylene 4->noid, ]-bi/' or propylene oxite) adducts thereof are included. Among these, those having 2 to 3 functional groups are preferred. Modified polyisocyanate and prepolymer free 1fgf [incyanate group content is usually 10 to 80%, preferably 15 to 30
%, particularly preferably 20 to 30%. Among the organic polyisocyanates, preferred is a mixture of I' I) l and crude MI) I (weight II, 1. ratio, for example 95.5-80, preferably 90.10-50:
50).

Examples of blowing agents include water and/or halogen-substituted aliphatic hydrocarbon blowing agents (trichloromonofluoromethane 41).
Which fluorocarbons can be used? Preferred is 131 water.

In the present invention, 45 has a free foam density of 0.02 to 0,
It is preferable to adjust the amount of blowing agent used so that it is within the range of 4 g/art.The free foam density is 0.
If it is less than 0.02g/a+I, the cells of the foam will become rough when it is made into a molded form, and if it is less than 0.04g/c
If the temperature is higher than ut, there will be more strong surface skin on the mold surface 1. The amount of foam stock solution injected into the mold 1 is preferably adjusted to a pack rate (excess filling rate) of 120 to 800%. That is, an amount 12 to 3 times the minimum required M (injection amount in the case of free foaming) of the foam stock solution calculated by the mold internal volume is injected. If the packing ratio is less than 120%, the mold form will become rough and the cells will collapse. When the pack rate exceeds 300%, the cells of the mall 1 form become fine and a strong cell film is formed.
There are many surface skins, poor air permeability and rapid foaming, and too much foaming pressure is applied, significantly reducing workability when pouring into a mold. Furthermore, if necessary, pigments, fillers, flame retardants, thixotropic agents, etc. may be added to the foam stock solution. In the present invention, the foam can be produced by a conventional mold foaming technique. For example, polyol is mixed with a foaming agent, a catalyst, a foam stabilizer, etc. to form liquid A, and liquid B is prepared in advance with organic f-socyanate L7 and filled into a tank of a low-pressure foaming machine. The foam obtained by open molding the polyurethane foam stock solutions (solutions A and B) with a mixing head can be further treated with an alkaline aqueous solution or by a combustion method to completely remove the surface skin and cell membrane. . Alkali include Na□II, Kol
l is mentioned. The concentration of the aqueous solution is usually 20-50%. The alkaline aqueous IF treatment can be carried out using conventional methods and conditions. For example, the mold form is 80-90
The film is removed by immersing it in an 8()% alkaline aqueous solution of C for 15 to 20 hours.

After foaming is completed, the mixture is poured into a curing oven at 80-150"C and removed from the mold after hardening.Isocyanate 1-
The index is usually 70-120, preferably 80-110.

Further, the combustion method (the combustion residue to be used is a mixture of propane, butane, etc. and oxygen), etc. can be mentioned. The mixing ratio (weight ratio) of propane and oxygen is usually 5.95 to 14:85. Film removal using the combustion method can be carried out using generally known methods and conditions.

For example, put the film in an airtight container and hold approximately 400 nH.
After reducing the pressure to g, a mixed gas of 7% propane and 98% oxygen was added to make it 760 mm and 11 g, and the mixture was ignited and burned to remove the film.

In the present invention, a conventional method for producing a porous ceramic drawing body using polyurini foam foamed in the presence of a silicone foam stabilizer represented by the general formula (]) and a tertiary amine is used. can be used, for example, JP-A-5
5 245851'4', JP-A-55-1] 1817 bow, JP-A-58-161962 bow, JP-A-58-9104
8 bow, and the one described in Japanese Patent Application Laid-Open No. 58-151.382.

The raw material of the ceramic slurry used for a-immersion is sintered to give the composition MgO, A (J20
．． .

Mixed powder containing 5i02, or the mixed powder described in 2 above, is heated to form causierite thread ceramics, which is then powdered.
It is preferable to use a binder such as vinyl alcohol, polyvinyl phthalate, or water, but it is not necessarily limited to these materials, and other known ceramic raw materials may also be used.
Good. Further, the firing treatment may be performed at a generally known temperature and time.

Preferably, the temperature is 1800 to 470"C for 5 to 6 hours.

In the present invention (second shot 1! IJ), the shape of the porous ceramic to be produced (1 columnar shape, elliptical columnar shape, etc. is generally used, but other end faces or curved 1h1 shapes are also used. The external shape is not limited.The cross-sectional shape of the columnar hollow hole formed inside the ceramic is circular, 11-hedral,
It can be configured into a square, a square, etc., but is not necessarily limited to these shapes. Further, the size and number of the hollow holes, the thickness of the hollow hole wall, and the thickness of the four peaks of the hollow holes can be arbitrarily selected.

The mold consists of a mold container part and a mold lid part, each having a cavity formed in a shape similar to that of the porous ceramic that is the intended product. Molding) (The container portions are provided in a lattice pattern at appropriate intervals with columnar members having approximately the same cross-sectional shape and length as the cross-sectional shape of the hollow holes opening in the same direction.On the other hand, the molding mold The lid part has approximately the same cross section and length as other hollow holes opening in the same direction, and is provided in a grid pattern at appropriate intervals. are combined in an interlocking manner to obtain the j1 polymorphism. At this time, the columnar members of the mold lid part fit into the space between the columnar members of the mold container part, and when the insides are assembled, the i
There is a suitable empty cavity in which the polyurethane foam stock solution described in i-1 should be prepared. This mold cavity has approximately the same shape as the porous ceramic that is the target manufactured article, and has a size that takes into account shrinkage due to firing, which will be described later. The foam stock solution is foamed in the mold configured in this manner.

In addition, the foaming process may be performed by assembling the molds and then injecting the foam stock solution.The foam stock solution is injected into the container part of the molding mold, and the lid part of the molding mold is immediately assembled, and the foam is foamed inside the molding machine to remove the excess. It is also possible to discharge the foam undiluted solution.

In addition, during foaming, the coarseness of the network of the rising porous ceramics can be freely adjusted according to the mixing ratio of the foaming agent, silicone foam stabilizer, catalyst, etc. The inside of the body is coated with a suitable mold release agent, and it is desirable to perform a surface treatment such as Teflon treatment so that the organic compound can be easily removed from the molded body after foaming.

〔Example〕

The manufacturing method of the present invention will be specifically explained below using Examples. In addition, parts or % in the examples are parts by weight or weight %.
represents.

Foam production example 1: Addition polymerization of 4258 g of propylene oxide to 92 g of glycerin, followed by addition of 650 g of ethylene oxide! molecule (i 5000 polyether polyol (B) 5
0 parts, 27 parts of water, 01 parts of triethylenediamine, 03 parts of N-ethylmorpholine, and foam stabilizer B for 50 parts of polymer polyol (A) obtained by polymerizing 20% of acrylonitrile based on this polyol. Add 8 parts of TI) I-80 and Crude MI to a premix containing 5 parts of -5246 (manufactured by Goldschmidt) + o, 'y.
Add 36 parts of isocyanate blended with 0.0 and 20 and stir and mix for 10 seconds at a speed of 11,000 RP. )
(manufactured by Ae), the lid was closed, and the mixture was foamed in the mold. After 3 minutes had passed after the completion of foaming, the mixture was cured in an oven at 1000°C for 45 minutes.

1-1 for the evaluation method below.
The nail, air permeability, and general mechanical properties of the surface skin cell membrane were investigated.

(Form's +i't' value method) 8. Surface - area of skin, mold form table, area of 1 stone is 1 (10), skin's area is 1n1
Kozu with nine. The smaller the area of the surface skin, the better the air permeability of the foam.

B. Cut the mold film of the cell membrane, observe the cell condition on the no-not surface with a magnifying glass, and find that there are 1iIlll cells with cell membranes in a length of 10mm! i Count and press % to see if there is any. The smaller the amount of cell membrane, the better the breathability.)・
It has a curving form with low pressure loss when used as an f filter.

C alk J treatment time: It shows the time it takes for the surface skin cell film to completely disappear when the treated Mole foam is immersed in a 30C4 alkaline aqueous solution of 20" C. The shorter the treatment time, the more complete the surface skin, Sugiru mold foam without cell membrane can be easily obtained.

■] Mechanical properties such as tensile strength, elongation, tear strength, compressive strength Jw, permanent set, air permeability, etc. are evaluated. A mold form with low mechanical strength is good as a cushion.

■・7. Internal collapse of the cell: The state of the RIS cell inside the mold form was observed. Cell collapse was determined when the cell skeleton collapsed and several cells were joined together.

1; The results of the test are shown in Table 2.

Foam production examples 2 to 8 Polymerization part polyol (8) and polyether polyol (Y
Example 1 was carried out in the same manner as in Example 1, except that the blending ratio with 5), water, 4t of catalyst (!-lyethylenecyamine, N-ethylmorpholine), type of o-conditioning agent, or overpack ratio were changed. .

The foaming formulation and evaluation results are shown in Tables 1 and 2, respectively.

Note that Foam Production Example 8 uses a silicone foam stabilizer that is outside the scope of the present invention.

Example I S') Force (S i02 ) 46%, 7 Jl/
i: t (A, e20B) 82% and ferrous oxide (F
e O) Talc (talc), kaolin and ferra-r1 blended to have a chemical composition of 22%
Formulation 1 consisting of ~ (ferrugolivine) (1 (1 part) and
A mixture of 60 parts of water, 1 part of C-C polyhydrinyl alcohol as a binder, and 1 part of a surfactant was mixed and stirred to form a slurry.

Boliu I/Tanoform obtained in Form Production Example 2 was impregnated into this, then pulled up and heated at 120° (j 1 to 3
Time 1 c] Dry. This operation was repeated two or three times to obtain a thick slurry deposited on the polyurethane foam skeleton.

Next Niji') l;IJ (S 102) 51%, 7
A mixture of talc, kaolin, and aluminum hydroxide blended to have a chemical composition of 35% Le E t (A, (J2C)B ) and % magnesia (MgO)H was made into a slurry in the same manner as described above. An Wt in this
Soak polyurethane foam in slurry - C to 1
It was dried at 20°C for 1 to 3 hours. This operation was repeated 2 to 3 times.

The slurry-free polyurethane foam obtained in the above procedure was fired at 1400''C for 8 hours to form a ceramic structure with a former mesh structure.

Example 2 Next, a specific method for producing a ceramic structure (filter material A) using the method of the present invention will be described below, including the structure of the foam matrix and the structure of the mold.

(1) 47.i of “Foam molded body and filter material”
Figure 1 (2I) shows a perspective view of the external appearance of the foam molded body and the filter material 20 (), and Figure 1 (1)) shows a cross-section 111Y of the main part outside the molding. The foam molded body and the filter material have a cylindrical shape as a whole, and the molded body has a large number of hollow holes 20 from its both ends (which do not intersect). has been set up J)su, -O:! Insert the li side into the 1" part 23, and exit the other end [
-1 part 24. Adjacent hollow holes 20 have their ends 22 closed and communicate with each other via partition walls 2 interposed between the hollow holes 20. This partition wall 21 has a three-dimensional network structure as shown in FIG.
12 so that air can pass through it. Note that the enlarged end portion 22 also has a structure as shown in FIG. 2, but its through hole 212 has become very small due to the foaming pressure.

(11) Molding mold structure Figure 3 shows the mold table 8H section used for manufacturing the above-mentioned foam molded body, Figure 8 (2I) is a plan view, and Figure 3 (1) is a sectional view. The mold container part I consists of an end face 5 and a side wall 2 to which a columnar member 3 having a small square cross section is vertically fixed, and the other end face If it is opened.

On the other hand, FIG. 4 shows a mold lid part combined with the mold container part 1, and FIG. 4(a) is a plan view, and FIG.
Figure (l) is a cross-sectional view. The mold lid part 10 is composed of a flat plate lid 15 to which a columnar member 13 is vertically fixed, similar to the J mold container part 1. The position of the columnar member 13 ('J position is
The columnar members 13 are attached to the grid-like sections that are not removed in the mold container part 1. Furthermore, one communication hole 16 is provided in each section of the flat plate of the mold lid 10, and a communication hole 17 is provided in the side periphery of the flat plate.

A mold is created by combining the mold container portion 1 and the mold lid portion 1o having such a configuration. FIG. 5 shows a cross section of the assembled mold.

Inside this mold, a cavity 8 having the same shape as the foam molded body to be manufactured is formed.

The mold lid 1O and the mold container 1 are removably fixed with screws 19 through a communication hole 17 provided on the side periphery of the mold lid 1o so that a predetermined combination can be achieved.

(:::) Production of foam molded article Now, a specific method for manufacturing a foam molded article using the mold having the above configuration will be described.

(a) 2.5 g of water, 0.15 g of N-ethyl morboline, Ethylenediamine (DABC
O) olog, n & foam agent B-5246 (j'-J
Add 10.5 g of Tosh Etl-fpH Co., Ltd. and 1-25 g of isocyanate, and stir and mix at a speed of 1000 rpm for 8 seconds. Apply a wax-based mold release agent (for example, uR1 manufactured by Honto Wax Co., Ltd.) to the mixture beforehand.
'851-) is applied to the inside (total coating amount: 15 g) of the mold shown in FIG.

Note that at this time, the air inside the mold flows through the remaining communication holes 1.
Ejected from 6, -1-Kiharane? I often inject liquid. In addition, injecting urethane foam i and t, the undiluted solution of urethane foam is injected into the mold container part 1, and then the mold lid part 10 is inserted, and the air and excess urethane foam in the mold are poured into the mold lid. It was also possible to create a structure in which the gas was discharged from a large number of communication holes 16 provided in the section 10.

Next, it is foamed in the cavity 18, and heated to 80"C for 15 minutes.
Heat and cure for ~60 minutes. Thereafter, the mold container part 1 and the mold lid part 10 are removed to obtain a foam molded body.

By the way, in one foam molding obtained in the same manner as in the case of a child, the foam stabilizer in the liquid described in II), the wax-based release agent r + and v agent on the mold surface, and the pressure during foaming. Therefore, the portions of the mold container portion 1 that are in contact with the columnar member 3 and the portions of the mold thin portion 10 that are in contact with the columnar member 13 are made film-free, so that
Column-like part a Δ3. Between the skeleton of the three-dimensional network structure in contact with I3 (3↑ skin (membrane) is no longer stretched,
Becomes breathable.

In addition, 1, sea urchin spacing Ji, ? The thickness of j21 is less than or equal to 20 mm (1 to 20111I)
In the case of I+), the cells of the foam collapse in the gap 11■ (mold space; see Figure 5) between the columnar parts 3 and 13 of the mold, but the coating on the inner surface of the mold The surface tension of the wax-based mold release agent can prevent it from collapsing, which greatly contributes to the formation of skinless foam.The mold shown in Fig. 5 has an expansion ratio of 1-
It has a structure with good sealing properties that are easy to peel off, and this also contributes to the formation of a skidless form.

Now, if necessary, the foam molded article produced as described above may be further heated in a 30% caustic sorter aqueous solution at 8°C to 12°C.
0°'' (approximately 5 to 30 I +
It has a cylindrical shape of 1'1mm, a square hollow hole with sides of 5IllIll (reference 120 in Figure 1), and a thickness of 8m.
A foam molded article was obtained which had a partition wall of m (?e'Q21 in FIG. 1) and a vent hole size of IO to 80 mesh.

(1) Here, an experimental example will be explained to demonstrate the advantages of the present invention. The test specimens had the structure shown in Figures 1 (a) and (b), with a diameter of 127 mm, a length of 110 mm, and a bulkhead thickness of 3 mm.
The dimensions are H, m, the size of the ventilation hole is 60 to 70 mesh, and the size of the hollow hole is a square with 41111111 sides. One of the test products was prepared by the above-mentioned method (a), and the other test products were conventional examples prepared without using the above-mentioned foam stabilizer and mold release agent. In addition, after molding, all of the above test products were heated to a temperature of 80''(': ~
16 in a 30% Na011 aqueous solution kept at 90°C
The skin (which is formed on each skeleton by time soaking)
After removing the thin film and thoroughly rinsing with water, it was dried for 2 to 4 hours.

The pressure loss situation when air is flowed through each test item is shown in Section 6.
As shown in the figure. As can be understood from FIG. 6, the product obtained by the method of the present invention has a significantly lower pressure loss and a remarkable skin removal effect than the conventional method.

In addition, in the method for manufacturing the molded foam product, the mold release agent used was URT-85T (trade name, manufactured by Bond Wax Co., Ltd.), but it changed from a solid phase to a liquid phase at a temperature of 80°C to 9°C. Any wax-based material that has good wettability with the surface of the mold may be used.

(i) Manufacture of ceramic structure Next, the foam molded body is immersed in a ceramic slurry made by stirring a powder mainly composed of Cor. After removing the slurry, it was heated and dried at 100 to 120°C, and this immersion and drying process was repeated several times. Then 1300-147
It was baked at about 0°C for about 5 hours.

An axial cross-sectional view of the porous ceramic thus obtained is shown in FIG. 1 (1)), and a partially enlarged view of its structure is shown in FIG. 2. The arrow in the figure indicates the traveling path of the exhaust gas. Exhaust scum flows from the ceramic part 1 23 into the hollow hole 2 (), passes through the porous hollow hole III, and then flows into the adjacent hollow hole 20.
-X flows out from the hollow hole river 1'' portion 24 to the outside of the ceramic. Carphone fine particles contained in the exhaust gas are mainly collected by the hollow hole wall 21. Also, sealing of the hollow hole fl 'X
II22 is made integrally with the hollow hole wall 21.

The outer diameter is 1.20mm and the length is 1.
A porous ceramic structure having a cylindrical shape of 50 mm, a square hollow hole with a side of 5, and a hollow hole wall with a thickness of 3,111,111 mm, and a roughness of #40 with a thickness of 1'' was manufactured. Using this porous ceramic, a test was conducted on the collection efficiency of carbon particles. Exhaust @22 driving conditions 11 modes, carbon particulate emissions are o,<g/mile,
The proportion of carbon trapped in porous ceramics is o,
s 5 g/mile, and a collection rate of 875% was obtained. Pressure loss is 2 under sasseta condition when air passes through 1m8/min.
cm II 20.

In addition, the collection rate was 75% in a porous ceramic structure produced from a foam molded body produced without using the above-mentioned foam stabilizer.
, the pressure loss was 8 an lI20 (air passage at 1 rn'/min).

I-Effects of the Invention 1 The production method of the present invention is clearly superior to the conventional production method of VL in the following points.

Using the general formula (1) used in the present invention, 7-<sallicorn, 1-foaming agent, 31, and tertiary amine catalyst-
(Compared to conventional polyurethane foam, polyurethane foam produced by mold foaming has fewer cell membranes, fewer surface skins, better air permeability, and a thinner cell skeleton.
Since the cells are aligned and there is little loss, when using this for 'IJQ construction' of porous ceramic structures, -c1 film removal treatment (alkali treatment, etc.) is significantly shorter than conventional ones ( (can be omitted).

With conventional foam, even after treatment with aqueous alkali solution, Ti
Ii! Cell collapse occurs when the cell membrane is not sufficiently removed from each skin, and if the alkaline aqueous solution treatment time is prolonged, the cell skeleton collapses and the foam loses its shape.Ii! However, the porous ceramic produced from this had a large pressure loss and had insufficient collection function and mechanical strength. Porous ceramic structures have less pressure loss, better collection function, and better mechanical strength than conventional structures.

The porous ceramic structure obtained in the present invention has a catalyst JUi
It is useful for applications such as heat-resistant filters, chemical-resistant filters, molten metal vortex bodies, gas diffusers, and fluid mixers.

The structure obtained according to the present invention (second invention) is particularly useful for collecting carbon fine particles contained in the exhaust scum of a "de-chill internal combustion engine W".

[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1(a) is a perspective view showing a foam filter obtained by the present invention, FIG. 1(b) is a sectional view of essential parts showing a cross section of the filter of FIG. 1(a), FIG. 2 is an organization diagram showing an enlarged view of the partition wall in FIG. 1(b), FIG. 4(a) and (l) are a plan view and a sectional view showing an example of a mold lid part for explaining the present invention, and FIG. 5 is a combination of FIGS. 3 and 4. A cross-sectional view showing the state
FIG. 6 is a characteristic diagram for explaining the present invention in detail. Figure 1(a) JP-A-1. YG1-155272 (13) Fig. 3 (a) Fig. 2 (b) Lo-lo-mesh RO ■ Lo-inner bolt - Fig. 4 (a) Fig. 5 (b) lb 1/ Procedure (Method) Patent Office Official Ugafu ISF, Died 1986 1E I
J"30r:]]Specific] No. 162729/1983, title of invention, method for manufacturing ceramic structures 3, person making corrections! 1. Amazing relationship Patent applicant 11. January 8, 1988 [1]" January 28, 1986)

Claims (1)

[Claims] 1. In producing a porous ceramic structure by adhering a ceramic slurry to an organic polymer foam, drying and firing, the foam contains an organic polyisocyanate and a polyol according to the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, A represents a polyoxyethylene and/or oxypropylene chain with an average molecular weight of 100 to 700, x represents 3 to 20, y represents 3 to 30, R represents H and/or an alkyl group having 1 to 5 carbon atoms and/or an acyl group. (However, the dimethylsiloxane units and polyoxyalkylenesiloxane units may be randomly arranged.) Polyurethane foam produced by mold foaming in the presence of a silicone foam stabilizer, a tertiary amine catalyst, and a blowing agent. A method for manufacturing a ceramic structure characterized by using. 2. The method according to claim 1, wherein the catalyst comprises a tertiary amine that promotes a resin-forming reaction and a tertiary amine that promotes a foaming reaction. 3. Polymer polyol (A) made of an ethylenically unsaturated monomer and a polyether polyol and/or a polyester polyol as at least a part of the polyol
, or (A) and a polyurethane foam using polyether polyol (B). 4. The foam has a free foaming density of 0.02-0.04g
Packing rate of foam stock solution that gives /cm^3 is 120 ~
The manufacturing method according to any one of claims 1 to 3, which is a polyurethane foam obtained by injecting the polyurethane foam into a mold in an amount of 300%. 5. Inside the ceramic, a plurality of parallel columnar hollow holes are provided so as to form a lattice-like arrangement in a cross section perpendicular to the axis of the hollow holes, and one end of the columnar hollow hole is opened at one end surface of the ceramic. A method for manufacturing a porous ceramic structure in which the other end is sealed at the other end face of the ceramic, and adjacent columnar hollow holes open in opposite directions across the hollow hole walls arranged in a lattice pattern. , a mold container portion consisting of an end face and a side wall to which a columnar member is fixed for forming a group of columnar hollow holes opening in the same direction, and the other end face is open; and the other columnar hollow hole opening in the same direction. The cavity of the mold formed by engaging the mold lid to which the columnar members for forming the group are fixed has the same shape as the above-mentioned ceramic, and in the mold cavity, the organic polyisocyanate and the polyol are generally mixed. Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) [In the formula, A represents a polyoxyethylene and/or oxypropylene chain with an average molecular weight of 100 to 700], x
represents 3 to 20, y represents 3 to 30, and R represents H and/or an alkyl group having 1 to 5 carbon atoms and/or an acyl group. (However, the dimethylsiloxane units and polyoxyalkylenesiloxane units may be randomly arranged.)] The shape is the same as that of ceramics by foaming in the presence of a silicone foam stabilizer, a tertiary amine catalyst, and a blowing agent. A method for producing a porous ceramic structure, comprising the steps of: obtaining a foam obtained in the step; and impregnating the foam obtained in the step with a ceramic slurry, drying and firing.